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Kinetic modeling of propene hydroformylation with Rh/TPP and Rh/CHDPP catalysts / Andreas Bernas in Industrial & engineering chemistry research, Vol. 47 N° 13 (Juillet 2008) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 47 N° 13 (Juillet 2008) . - p. 4317–4324 Titre : Kinetic modeling of propene hydroformylation with Rh/TPP and Rh/CHDPP catalysts Type de document : texte imprimé Auteurs : Andreas Bernas, Auteur ; Paivi Maki-Arvela, Auteur ; Juha Lehtonen, Auteur ; Tapio Salmi, Auteur Année de publication : 2008 Article en page(s) : p. 4317–4324 Note générale : Bibliogr. p. 4324 Langues : Anglais (eng) Mots-clés : Propene  hydroformylation;  Solubility;  Rhodium/triphenylphosphine  catalysts Résumé : Hydroformylation of propene to isobutyraldehyde and n-butyraldehyde was studied in the kinetic regime in a semibatch stainless steel reactor at 70−115 °C and 1−15 bar overpressure in 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate solvent with rhodium/cyclohexyl diphenylphosphine (Rh/CHDPP) and rhodium/triphenylphosphine (Rh/TPP) catalysts. The influence of process parameters such as Rh concentration (50−250 ppm), ligand mass fraction (0−10 wt %), H2-to-CO ratio, and stirring power was investigated and the influence of solvent concentration was studied by using mixtures of valeraldehyde and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as solvent. The solubility of propene, H2, and CO in 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate was measured in the same reactor. Rh/CHDPP showed lower normal/isometric aldehyde ratio (n/i) than Rh/TPP. The rate was temperature and pressure dependent, while the Rh concentration or syngas composition did not have any significant impact. The n/i ratio was always independent of the conversion, but dependent on the ligand concentration: higher ligand concentration promoted isobutyraldehyde formation. Based on experimentally recorded kinetic data, a stoichiometric scheme was proposed and parameters of power-law rate models were determined by using nonlinear regression analysis. The experimental system was described as a perfectly mixed gas−liquid reactor. As showed by sensitivity analysis, the kinetic parameters were well identified and physically reasonable and they were in accordance with qualitative observations. The kinetic models with a degree of explanation of more than 0.9 described the formation of the products with satisfying accuracy. En ligne : http://pubs.acs.org/doi/abs/10.1021/ie071401r [article] Kinetic modeling of propene hydroformylation with Rh/TPP and Rh/CHDPP catalysts [texte imprimé] / Andreas Bernas, Auteur ; Paivi Maki-Arvela, Auteur ; Juha Lehtonen, Auteur ; Tapio Salmi, Auteur . - 2008 . - p. 4317–4324. Bibliogr. p. 4324 Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 47 N° 13 (Juillet 2008) . - p. 4317–4324 Mots-clés : Propene  hydroformylation;  Solubility;  Rhodium/triphenylphosphine  catalysts Résumé : Hydroformylation of propene to isobutyraldehyde and n-butyraldehyde was studied in the kinetic regime in a semibatch stainless steel reactor at 70−115 °C and 1−15 bar overpressure in 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate solvent with rhodium/cyclohexyl diphenylphosphine (Rh/CHDPP) and rhodium/triphenylphosphine (Rh/TPP) catalysts. The influence of process parameters such as Rh concentration (50−250 ppm), ligand mass fraction (0−10 wt %), H2-to-CO ratio, and stirring power was investigated and the influence of solvent concentration was studied by using mixtures of valeraldehyde and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as solvent. The solubility of propene, H2, and CO in 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate was measured in the same reactor. Rh/CHDPP showed lower normal/isometric aldehyde ratio (n/i) than Rh/TPP. The rate was temperature and pressure dependent, while the Rh concentration or syngas composition did not have any significant impact. The n/i ratio was always independent of the conversion, but dependent on the ligand concentration: higher ligand concentration promoted isobutyraldehyde formation. Based on experimentally recorded kinetic data, a stoichiometric scheme was proposed and parameters of power-law rate models were determined by using nonlinear regression analysis. The experimental system was described as a perfectly mixed gas−liquid reactor. As showed by sensitivity analysis, the kinetic parameters were well identified and physically reasonable and they were in accordance with qualitative observations. The kinetic models with a degree of explanation of more than 0.9 described the formation of the products with satisfying accuracy. En ligne : http://pubs.acs.org/doi/abs/10.1021/ie071401r